JPH0776300B2 - Polyamide resin blow molding container - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to a hollow molded container based on a polyamide resin. Polyamide resins are used in a wide range of fields by taking advantage of their excellent mechanical properties and heat resistance. However, polyamide resins such as nylon 6 and nylon 6,6 have the drawback of being inferior in impact resistance.

[Conventional technology]

It is known to copolymerize a dimerized fatty acid for the purpose of improving impact resistance and water resistance of a polyamide resin (JP-A-54-71191).

However, when blow molding is performed to obtain a hollow container from this, it is extremely difficult to obtain a product having a uniform thickness because the drawdown is large and the thickness is apt to be uneven.

[Object of the Invention]

The present inventors have conducted extensive studies in order to improve the above-mentioned problems, and as a result, a polyamide resin using a dimerized fatty acid as a copolymerization component was blended with a specific olefin polymer to significantly improve blow moldability. The present invention has been achieved by finding that it is possible to improve the mechanical properties and also improve the mechanical properties.

That is, according to the present invention, the main component is polycapramide or polyhexamethylene adipamide, and the content of dimerized fatty acid in the copolymer is 0.1 to 40% by weight. Copolymerized polyamide resin (A) 60 to 97 %, And a resin composition comprising 40 to 3% by weight of an olefin polymer (B) having a flexural modulus of 100 to 15000 kg / cm ² obtained by copolymerizing or modifying an α, β-unsaturated carboxylic acid or its derivative. The present invention provides a blow-molded container having as a base material.

[Structure of Invention]

 Hereinafter, the present invention will be specifically described.

The copolyamide resin of the component (A) in the present invention is obtained by polycondensing polycapramide or polyhexamethyleneadipamide whose main component is ε-caprolactam, or adipic acid, dimerized fatty acid and hexamethylenediamine. The content of dimerized fatty acid in the polymer is 0.1 to 40% by weight.

The dimerized fatty acid which is a copolymerization component is a fatty acid, for example, a polymerized fatty acid obtained by polymerizing a saturated, ethylenically unsaturated, acetylene unsaturated, natural or synthetic-basic fatty acid having 8 to 24 carbon atoms. . Specific examples thereof include a dimer of linolenic acid.

Commercially available polymerized fatty acid usually contains dimerized fatty acid as a main component and also contains raw material monomeric acid and trimerized fatty acid, but the dimerized fatty acid content is 70% by weight or more. Those are preferable. Further, commercially available polymerized fatty acid may be used by distilling it to increase the content of dimerized fatty acid.

The content of dimerized fatty acid in the polyamide resin is 0.1-40
%, Preferably 0.5 to 35% by weight.

If it is less than 0.1% by weight, impact resistance is poor, and if it is more than 40% by weight, moldability is poor.

The dimerized fatty acid is blended so that the carboxyl group and the amino group are balanced as a whole. Therefore, it is appropriately adjusted with an amine compound such as hexamethylenediamine.

At the time of polycondensation in the production of the copolyamide resin, other lactams, amino acids, dibasic acids, diamines and the like may be added to the above raw materials. These include enantolactam,
Lactams such as capryllactam, lauryllactam, α-pyrrolidone, α-piperidone, ω-amino acids such as 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid and 11-aminoundecanoic acid,
Glutaric acid, pimelic acid, suberic acid, azelaic acid,
Sebacic acid, undecanedioic acid, dodecadioic acid, hexadecadiodioic acid, hexadecenedioic acid, eicosandioic acid, eicosadiendioic acid, diglycolic acid,
Dibasic acids such as 2,2,4-trimethyladipic acid, xylylenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid and isophthalic acid, tetramethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylene Diamine, 2,2,4 (or 2,4,
4) -trimethylhexamethylenediamine, bis- (4,
4'-aminocyclohexyl) methane, diamines such as metaxylylenediamine, and the like.

Next, the olefin polymer obtained by copolymerizing the α, β-unsaturated carboxylic acid or the derivative thereof as the component (B) or modified with the copolymer will be described.

α, β-Unsaturated carboxylic acid or its derivative 3 to 12
Ethylenically unsaturated mono- or dicarboxylic acids having 1 carbon atom, and monocarboxylic acids with alcohols of 1 to 29 carbon atoms, dicarboxylic acid diesters and monoesters of dicarboxylic acids, and 0-100% of the carboxylic acid groups. Metal salts of monocarboxylic acids, dicarboxylic acids, and monoesters of dicarboxylic acids that have been ionized by neutralization with metal ions.

Specifically, metals such as methyl methacrylate, butyl acrylate, ethyl acrylate, alkyl esters of acrylic acid and methacrylic acid, sodium methacrylate, zinc methacrylate, maleic acid, maleic anhydride, maleic acid monoethyl ester, maleic acid monoethyl ester. Salts, fumaric acid, fumaric acid monoethyl ester, metal salts of fumaric acid monoethyl ester, maleic acid, fumaric acid alkyl monoesters having up to 29 carbon atoms, glycidyl methacrylate, glycidyl acrylate and the like.

These α, β-unsaturated carboxylic acids or derivatives thereof may be randomly copolymerized with monomers such as ethylene, propylene and butene, and may be graft-polymerized or graft-reacted with olefin polymers such as ethylene, propylene and butene. It may be done.

Specific examples of the olefin polymer useful in the present invention include the following random copolymers or graft products. That is, zinc salt of ethylene / methacrylic acid or methacrylic acid: zinc salt of ethylene / isobutyl acrylate / methacrylic acid: monoethyl ester of ethylene / methyl acrylate / maleic anhydride and zinc, sodium or calcium neutralized from 0 to 100% thereof. , Lithium, antimony, and potassium salts: ethylene / propyne / g-
Maleic anhydride: ethylene / butene / g-maleic anhydride: ethylene / methyl acrylate / methacrylic acid and its zinc salt: ethylene / vinyl acetate / methacrylic acid and its zinc salt: ethylene / propylene / 1,4-hexadiene
/ g-maleic anhydride: ethylene / propylene / norbornadiene / g-maleic anhydride: ethylene / propylene /
Tetrahydroindene / g-fumaric acid: ethylene / glycidyl methacrylate: ethylene / vinyl acetate / glycidyl methacrylate: ethylene / propylene / g-tetrahydrofurfuryl methacrylate: ethylene / butene / g-
Tetrahydrofurfuryl methacrylate: ethylene / propylene / g-maleic anhydride / g-tetrahydrofurfuryl methacrylate: ethylene / butene / g-maleic anhydride / g-tetrahydrofurfuryl methacrylate (g means graft) and the like. .

If the α, β-unsaturated carboxylic acid or its derivative is randomly copolymerized, the amount may be 50% by weight or less based on the total amount of all components, and the amount may be 0.01 to 2% by weight for grafting. As the modified olefin polymer, one having a certain degree of flexibility has a remarkable effect of improving impact resistance, and therefore has a flexural modulus of 100 to 150.
00 kg / cm ² , and more preferably 200 to 8000 kg / cm ² .

Such a modified olefin polymer is blended in the resin composition at a blending ratio of 60 to 97% by weight of the copolyamide resin (A) and 40 to 3% by weight of the modified olefin polymer (B).

When the content of the modified olefin polymer is less than 3% by weight, the effect of improving the moldability and mechanical properties is not observed,
When it exceeds 40% by weight, heat resistance and mechanical properties are remarkably deteriorated.

The compounding is performed by a method well known to those skilled in the art, and for example, melt kneading is performed by using an extruder, a super mixer, a Banbury mixer, or the like.

The resin composition, various additives well known to the above copolymer polyamide resin and modified olefin polymer, for example, glass fiber, carbon fiber, reinforcing agents such as metal whiskers, silica, alumina, silica-alumina viscosity mineral, Silica
Fillers such as magnesium-based clay minerals, calcium silicate, calcium carbonate, asbestos and carbon black, and other lubricants, nucleating agents, antioxidants, flame retardants, antistatic agents, weather resistance imparting agents, etc. may be contained. .

This resin composition is blow molded (hollow molding) by a usual method to obtain a hollow container.

〔Example〕

 Hereinafter, the present invention will be specifically described with reference to examples.

[Manufacture of copolyamide] 200 autoclave, ε-caprolactam 60k
g, 4.0 kg of water, 0.5 kg of polymerized fatty acid mainly composed of dimerized fatty acid (Empol 1014; trade name, manufactured by Unilever Emery Co., Ltd.), 0.125 kg of 80 wt% hexamethylenediamine aqueous solution, and nitrogen atmosphere 270 ℃
The temperature was raised to 14 kg / cm ² , the pressure was increased, and the pressure reaction was performed for 3 hours with stirring. Then, the pressure was gradually released to the degree of pressure reduction shown in the table, and 2
The reaction was performed under reduced pressure for an hour. Stop stirring, introduce nitrogen,
After returning to normal pressure, it was extracted as a strand and pelletized, unreacted monomer was extracted and removed using boiling water, and vacuum drying was performed.

The same procedure was followed except that the amount of polymerized fatty acid was 4.0 kg and the 80 wt% hexamethylenediamine aqueous solution was 1.0 kg.

50 kg of ε-caprolactam, 20 kg of polymerized fatty acid, 80
The same procedure was followed except that the weight% hexamethylenediamine aqueous solution was 5.0 kg.

Examples 1 to 8 The copolyamide resins described above and the olefin polymers shown in Table-1 were mixed in the composition shown in Table-1 to give 30 mm.
A φ2-screw extruder was used to melt and mix the resin within a temperature range of 220 to 270 ° C. to obtain pellets. The pellets obtained in this way are 30 mm in diameter with an extrusion blow molding machine with a cylinder diameter of 40 mm.
Using a φ die, blow-mold a hollow container with a length of 300 mm and a diameter of 80 mm.
The wall thickness of the 20 mm part was measured.

Further, 300 cc of water was added to the blow-molded product thus obtained and repeatedly dropped from a height of 1 m on the concrete floor, and the number of times until the hollow container was broken was measured.

The results are shown in Table-1.

Comparative Examples 1 to 3 The same processes as in Examples 1 to 8 were carried out except that the olefin copolymer was not added.

The physical property measurement results are shown in Table 1.

Comparative Examples 4 to 5 As a polyamide resin, a commercially available nylon 6 resin having a relative viscosity of 2.5 measured by Ostwald viscometer (manufactured by Mitsubishi Kasei Co., Ltd., N
ovamid 1010: trade name) was used in the same manner as in Examples 1 to 8 with and without the ethylene / methacrylic acid / zinc methacrylate copolymer as the olefin polymer.

Table 1 shows the blended composition and the physical property measurement results.

[Effects of the Invention] As described above, the blow-molded article using the resin composition of the present invention as a base material has a uniform wall thickness and high resistance to a drop test.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-60-170664 (JP, A) JP-A-55-12082 (JP, A) JP-A-59-59745 (JP, A) JP-A-56- 92954 (JP, A) JP 61-188479 (JP, A) JP 47-9903 (JP, B1)

Claims (1)

[Claims] 1. A copolymerized polyamide resin (A) having a content of dimerized fatty acid of 0.1 to 40% by weight in the copolymer, the main component of which is polycapramide or polyhexamethylene adipamide. %, And a resin composition comprising 40 to 3% by weight of an olefin polymer (B) having a flexural modulus of 100 to 15000 kg / cm ^{2 which} is obtained by copolymerizing or modifying an α, β-unsaturated carboxylic acid or its derivative. Blow molded container as a base material.